Cupric catalyst



United States Patent 3,247,234 CUPREC CATALYST Earl A. Ehach, Edward P. Merica, and Joseph C. Valenta,

Midland, Mich, assignors to The Dow Chemical Company, Midland, Mich., a corporation of Delaware No Drawing. Filed Oct. 3, 1961, Ser. No. 142,486 2 Claims. (6]. 260-433) The present invention relates to certain novel catalysts and more particularly concerns a class of catalysts having one of the following general formulas:

wherein R represents an aliphatic radiacl containing more than two carbon atoms, R represents an aromatic radical of the benzene series or naphthalene series, n represents an integer from 1 to 5, a represents an integer from 0 to 2, inclusive, p represents an integer from 0 to 5, b represents a number from 1 to 2 when p is 0, 1 to 3 When p is 1, 1 to 3+p when p is greater than 1 and X represents chlorine or bromine (i.e., a halogen having an atomic number from 17 to 35). These novel compounds have been found to be useful as a catalytic source of copper in, for example, the caustic hydrolysis of aromatic halides or the Ullmann ether synthesis and the like. It has been further observed that the copper salts of this invention promote or otherwise improve the character of the copper, reduce deposit build-up on reactor walls and materially reduce the quantity of copper required.

The new compounds are prepared by reacting a copper, cuprous or cupric compound or mixtures thereof with alkylated aromatic sulfonate having one of the generic wherein the symbols R, R, n, a, b, and p have the values assigned in Formulas I and H and M represents a member selected from the group consisting of hydrogen and an alkali metal. The reaction proceeds readily at from below room temperature to about100 C. The reactants are preferably employed in stoichiometrc amounts although exoess copper compound can be used to insure complete reaction when the product is to be isolated. Less than stoichiometric amounts of copper result in a product containing an excess of the sul fonate or sulfonic acid reactant which is difiicult to remove from the copper salt. However, the presence of such excess of the s-ulfonate or sulfonic acid reactant does not prevent the product from being effectively used as a catalyst, for example, in the hydrolysis of haloaromatic compounds, or Ullmann ether synthesis and although not normally desired it can be tolerated.

It is to be understood that substantially any watersoluble alkylated aromatic sulfonic acid or alkali metal 3,247,234 Patented Apr. 19, 1966 salt falling within the generic Formulas III and IV can be employed to prepare the copper salt. Thus one can employ the alkylbenzene sultonic acids and disulfonic acids, their nuclearly halogenated derivatives or their alkali metal salts such as propylbenzene sulfonic acid, propyl monochlorobenzene sulfonic acid, hexylbenzene sulfonic acid, hexyldibromobenzene sulfonic acid, nonylbenzene sulfonic acid, sodium nonylbenzene sulfonate, dodecylbenzene disulfonic acid, pentadecylmonochlorobenzene disulfonic acid and the like as well as their potas-,

sium, lithium, sodium and cesium salts; the alkylnaphthyl monoand disulfonic acids, their nuclearly halogenated derivatives or their alkali metal salts such as propylnaphthyl sulfonic acid, butylmonochloronaphthyl disulfonic acid, sodium dodecyldibromonaph-thyl disulfonic acid and the like as Well as their potassium, lithium, sodium, or cesium salts; the alkyl diand polyphenyl oxide monoand polysulfonic acids, their nuclearly halogenated derivatives and their alkali metal salts such as, for example, dodecyldiphenyl oxide sulfonic acid, nonylmonobromodiphenyl oxide disulfonic acid, sodium pentadecylphenoxydiphenyl oxide trisulfonate, potassium dodecylmonochloro bis(phenoxy)diphenyl oxide tetrasulfonate and the like as well as their potassium, lithium, sodium and cesium salts.

The source of copper reactant can be copper or any copper compound such as copper oxide (CuO), copper nitrate (Cu(NO cuprous oxide (Cu O), and the like as well as cupric and cuprous mixtures.

'It is to be further understood that the copper salt can be prepared by reacting the alkylated aromatic sulfonic acid with copper in the presence of strong caustic. This embodiment is more fully disclosed in the following examples.

The following examples illustrate the present invention but are not to be construed as limiting:

Example 1 Cupric oxide, grams (1.35 moles), was added with stirring to a solution of 468 grams (0.94 mole) of dodecyldiphenyl oxide disulfonic acid in 2430 ml. of water. Stirring was continued until a constant pH was observed. The final pH of the solution was 4.7. The resulting solution was filtered to remove the excess copper oxide and the filtrate, a dark green liquid, was dried on a rotating drum dryer to obtain an olive green powder. As a result of these operations there was obtained 475 grams (0.85 mole) of copper dodecyldiphenyl oxide disulfonate representing a 90.5% conversion of the sul-fonic acid to the copper salt.

Example 2 In a manner like that of Example 1, by substituting nonylbenzene sulfonic acid for the dodecyldiphenyl oxide disulfonic acid, there was obtained the copper di(nonyl benzene sulfonate) in near quantitative yields.

Other copper salts can be prepared by reacting:

Nonylnaphthy-l sulfonic acid with copper oxide to obtain copper d-i(nonylnaphthyleue sulfonate); or

Octadecyldiphenyl disulfonic acid with copper oxide to obtain copper octadecyld-iphenyl disulfonate.

Example 3 Copper powder (255 grains) was added with stirring to 33 grams of sodium dodecyldiphenyl oxide disulfonate in 63.8 pounds of 20% aqueous sodium hydroxide. The resulting blue solution was filtered to remove excms copper powder. The solution analyzed ca. 0.017% copper. This solution was used as a catalyst-containing composition in the caustic hydrolysis of halogenated aromatics in the manner of Example 4 (5).

Example 4 The following table illustrates the utility of the copper compounds prepared above as catalytic sources of copper in the caustic hydrolysis of halo diphenyl oxides. I

whereas when copper dust was substituted, 5 g. as catalyst, a sludge formed and yields were no better than here obtained.

Thus it becomes evident that good yields and conver- The reactants below were run in one of the following 5 sions. are obtainjc'd using the catalyst of the present pieces of equipment. vention employmg much less copper than heretofore Reactor (A): A five-inch diameter four foot long Monel thought PHI-flier I reqmres lmle pressure reactor fitted with a stirrer and appropriate f attenfilon a clealgimg to remove the inlets and outlets, valves and recorders -for controlling s Ti asw encopper q er h flow, and jacketed to provide heating and cooling means 10 new copper'comammg y? provlded by Q to control the temperature of the reaction medium. mvenpon be employ.ed wnh Slm'llar advantages Reactor (B): A one-eighth inch nominal diameter stainfzarrymg the hydrolysis. of halgarommlc Compounds less steel coil 500 feet long, jacketed to provide heating general m aqueolls alkahne F F9 they and cooling means to control the temperature of the reacbe employed h Y F Cami/mg out f medium. sis of the rnonoor di-'hal1des, 1.e., chlorides or bromines, The reactants, monobromodiphenyl oxide, aqueous of bellzene to i oxide catchol or sodium hydroxide and copper catalyst (as copper resorcmol i 9 1n carrying out the llydrolyslspf the powder), copper salt of an alkylated diphenyl oxide diq and (ohlondes bromlqajs) of dlphenyl sulfonate, or the 0 caustivcwdisulfonate premix) oxides [to produce phenoxyphenol, oxydipnenyl and biswere fed to the reactor at the flow rate indicated and the 20 fi z' f bi temperature controlled by heating or cooling. For pura y at.d enyl oxide Sulfonates gmgployed as poses of comparison, certain of the runs were made in the f mammals to l the copper Salts of the present absence of a copper-containing catalyst. The mole ratio Invemlon are Well known m The alkylated poly' of caustic to bromodiphenyl oxide was 2.2 to 1 in each phenyl ether Sulfonates such as alkylated blswhenoxw run. The conditions of the reaction, form of copper catabenzepe sulfonaic can prepared the salme manner as lyst and amount thereof as free or combined metallic {hp hens/.1 Oxlde slllfonates' By employing the copper, temperature, flow rate and products produced are prime Stamng mammal? Such as or examp 16 a .sodlum set forth below: phenolate and a halo diphenyl oxide then alkylatlng and Catalyst, g. Cu/lOO Temp., Flow Rate, Reactor DPOOH1 4P3E2 Total Remarks g. Br in BrDPO C. Lbs/Hr.

(1) None 320 148 B 17.2 0 17.2 280 72 A 25.4 10.7 36.1

338 85 A 6.2 Sludjge) in reactor.

i lOI i 89:9 N0 sludge. 327 107 A 37.9 37.4 75.3 D0.

1 DPOOHHydroxy diphenyl oxide. 2 4P3EBis(phen0xy)diphenyl oxide. 3 Copper powder. 4 Premix of Example 3. 6 Copper salt of dodecyldiphenyl oxide disulfonate of Example 2.

The following example illustrates the use of the copper sulfona-ting say in the manner of U.S. Patent No. 2,081,- cornpounds of the present invention as the catalytic copper 876. source in the Ullm'ann ether symthesis. We claim:

1. Copper dodecyldiphenyl oxide disulfonate. Example 5 2. A copper salt of alkyl sulfonated diphenyl oxide having the formula Dry potassium phenoxyphenate is prepared by heating a mixture of 433 g. 2.3 moles) of hydroxydiphenyl oxide 0 'l and 145 g. (2.2 moles) of 85% potassium hydroxide pelalkyl o lets at 150 with stirring, until the water formed in the L I react-ion has all come off. Ten g. of copper salt of do- 1 decyl monochloro diphenyl oxide sulfonate (prepared in wherein the symbol alkyl represents a radical having more the manner of Example 1) is then added and the temperathan two carbon atoms, b represents an integer from 1 ture is raised to 220-225. 236 g. (1 mole) of dibromoto 3. benzene is added dropwise at a rate which causes rapid References Cited by the Examiner reflux (.the reaction is quite vigorous and the condenser UNITED STATES PATENTS must be ample). Heating is continued at 225 for two hours after dibromobenzene addition is finished. The 2,081,876 3/1937 Pram 260-512 crude reaction mixture is then cooled to about 80, 2,555,371 6/1951 Prutton 260438 passed through a filter (it can be diluted with toluene if it 2,794,829 6/1957 Waarden et 260438 is too viscous), and washed with an equal volume of 2,864,742 12/1958 whtstone et 260 438 water, which removes the KBr and unreacted potassium 3,024,285 3/1962 l at 260 613 phenoxyphenate. To remove phenolic compounds, it is 3,025,322 3/1962 Smolm 260438 then washed With /2 its volume of 25% NaOI-I. Separa- 60 3,042,695 7/1962 Horn 260438 tion is aided by adding water until the caustic concentra- 3,051,736 8/1962 P 260-438 tion is about 5%. The washed organic material is then 3,056,842 10/1962 Vlnars distilled. There was obtained a ield of ca. of bis- (phenoxyphenoxy)benzene'based on dibromobenzene con- TOBIAS LEVOW Pmnmry Examme'l' sumed. No sludge was apparent in the reaction mixture CHARLES B. PARKER, Examiner. 

2. A COPPER SALT OF ALKYL SULFONATED DIPHENYL OXIDE HAVING THE FORMULA 